Gas-liquid-liquid reaction engineering: the Koch synthesis of pivalic acidfrom iso- and tert-butanol; Reaction kinetics and the effect of a dispersed second-liquid phase
Dwf. Brilman et al., Gas-liquid-liquid reaction engineering: the Koch synthesis of pivalic acidfrom iso- and tert-butanol; Reaction kinetics and the effect of a dispersed second-liquid phase, CHEM ENG SC, 54(21), 1999, pp. 4801-4809
In gas-liquid-liquid reaction systems with fast parallel and consecutive re
actions the effects of mass transfer and mixing on the product yield can be
significant. The Koch synthesis of pivalic acid, using sulfuric acid as ca
talyst, was chosen to study these effects. Reaction kinetics and the effect
of the catalyst-phase composition have been investigated by using isobutan
ol as reactant. For studying the effect of an immiscible liquid phase on th
e reaction products obtained, the more reactive tert-butanol was used. Piva
lic acid can be produced from isobutanol using sulfuric acid as a catalyst
solution with 2-methylbutanoic acid as main byproduct, if gas-liquid mass t
ransfer limitations are excluded. The selectivity towards 2-methylbutanoic
acid is generally less than 20% and decreases strongly with decreasing acid
ity. The reaction is first order in isobutanol and dehydration is likely to
be rate determining. The presence of pivalic acid and isobutanol strongly
reduces the apparent reaction rate constant by decreasing the solution acid
ity (Ho). For the industrially applied backmixed reactors in the Koch synth
esis, this may imply that these operate at much lower values for Ho. On add
ition of an immiscible heptane phase, the reaction products are extracted t
o some extent and this adds to maintaining a high catalyst solution acidity
. Using tert-butanol, the yield and pivalic acid selectivity was found to d
epend strongly on CO transport to the reaction zone through gas-liquid mass
transfer and mixing. The presence of an immiscible heptane phase increased
the product yield and selectivity towards pivalic acid significantly. (C)
1999 Elsevier Science Ltd. All rights reserved.